Carbon.Nanotubes.pdf

Foreword

by R. E. Smalley, Chemistry Nobel Lauveate 1996

Since the discovery of the fullerenes in 1985 my research group and I have

had the privilege of watching from a central location the worldwide scientiﬁc

community at work in one of its most creative, penetrating, self-correcting,

and divergent periods of the last century. In his recent book, “The Transpar-

ent Society”, David Brin discusses the virtues of an open, information rich

society in which individuals are free to knowledgeably criticize each other,

to compete, to test themselves and their ideas in a free market place, and

thereby help evolve a higher level of the social organism. He points out that

modern science has longfunctioned in this mode, and argues that this open

criticism and appeal to experiment has been the keystone of its success. This

new volume, Carbon Nanotubes, is a wonderful example of this process at

work.

Here you will ﬁnd a summary of the current state of knowledge in this

explosively growing ﬁeld. You will see a level of creativity, breadth and depth

of understandingthat I feel conﬁdent is beyond the capability of any single

human brain to achieve in a lifetime of thought and experiment. But many

ﬁne brains workingindependently in the open society of science have done it

very well indeed, and in a very short time.

While the level of understandingcontained in this volume is immense, it

is clear to most of us workingin this ﬁeld that we have only just begun. The

potential is vast. Here we have what is almost certainly the strongest, stiﬀest,

toughest molecule that can ever be produced, the best possible molecular

conductor of both heat and electricity. In one sense the carbon (fullerene)

nanotube is a new man-made polymer to follow on from nylon, polypropylene,

and Kevlar. In another, it is a new “graphite” ﬁber, but now with the ultimate

possible strength. In yet another, it is a new species in organic chemistry, and

potentially in molecular biology as well, a carbon molecule with the almost

alien property of electrical conductivity, and super-steel strength.

VI Foreword

Can it be produced in megatons?

Can it be spun into continuous ﬁbers?

Can it grown in organized arrays or as a perfect single crystal?

Can it be sorted by diameter and chirality?

Can a single tube be cloned?

Can it be grown enzymatically?

Can it be assembled by the molecular machinery of livingcells?

Can it be used to make nanoelectronic devices, nanomechanical memories,

nano machines,

...

There is no way of tellingat this point. Certainly for many researchers, the

best, most excitingdays of discovery in this ﬁeld are still ahead. For the

rest of us, it will be entertainingjust to sit back and watch the worldwide

organism of science at work. Hold on to your seats! Watch the future unfold.

Houston, Texas

January 2001

Richard E. Smalley

Canitbeusedtowireabrain?

Preface

Carbon nanotubes are unique nanostructures with remarkable electronic and

mechanical properties, some stemmingfrom the close relation between car-

bon nanotubes and graphite, and some from their one-dimensional aspects.

Initially, carbon nanotubes aroused great interest in the research community

because of their exotic electronic structure. As other intriguing properties

have been discovered, such as their remarkable electronic transport proper-

ties, their unique Raman spectra, and their unusual mechanical properties,

interest has grown in their potential use in nanometer-sized electronics and

in a variety of other applications, as discussed in this volume.

An ideal nanotube can be considered as a hexagonal network of carbon

atoms that has been rolled up to make a seamless hollow cylinder. These hol-

low cylinders can be tens of micrometers long, but with diameters as small as

0.7nm, and with each end of the longcylinder “capped with half a fullerene

molecule, i.e., 6 pentagons”. Single-wall nanotubes, having a cylindrical shell

with only one atom in thickness, can be considered as the fundamental struc-

tural unit. Such structural units form the buildingblocks of both multi-wall

nanotubes, containingmultiple coaxial cylinders of ever-increasingdiameter

about a common axis, and nanotube ropes, consistingof ordered arrays of

single-wall nanotubes arranged on a triangular lattice.

The ﬁrst reported observation of carbon nanotubes was by Iijima in 1991

for multi-wall nanotubes. It took, however, less than two years before single-

wall carbon nanotubes were discovered experimentally by Iijima at the NEC

Research Laboratory in Japan and by Bethune at the IBM Almaden Labora-

tory in California. These experimental discoveries and the theoretical work,

which predicted many remarkable properties for carbon nanotubes, launched

this ﬁeld and propelled it forward. The ﬁeld has been advancingat a breath-

takingpace ever since with many unexpected discoveries. These excitingde-

velopments encouraged the editors to solicit articles for this book on the

topic of carbon nanotubes while the ﬁeld was in a highly active phase of

development.

This book is organized to provide a snapshot of the present status of this

rapidly movingﬁeld. After the introduction in Chap. 1, which provides some

historical background and a brief summary of some basic subject matter

and deﬁnitions, the connection between carbon nanotubes and other carbon

materials is reviewed in Chap. 2. Recent developments in the synthesis and

VIII Preface

puriﬁcation of single-wall and multi-wall carbon nanotubes are discussed in

Chap. 3. This is followed in Chap. 4 by a review of our present limited un-

derstanding of the growth mechanism of single-wall and multi-wall carbon

nanotubes. Chapter 5 demonstrates the generality of tubular nanostructures

by discussing general principles for tubule growth, and providing the reader

with numerous examples of inorganic nanotube formation. The unique elec-

tronic structure and properties of perfect and defective carbon nanotubes are

reviewed from a theoretical standpoint in Chap. 6. The electrical properties,

transport, and magneto-transport measurements on single-wall nanotubes

and ropes, as well as simple device structures based on carbon nanotubes are

presented in Chap. 7. Scanningtunnelingmicroscopy is used to study that

nanotube electronic structure and spectra. The use of nanotubes as atomic

force microscope tips for ultra-high resolution and chemically sensitive imag-

ingis also discussed in Chap. 8. The application of optical spectroscopy to

nanotubes is presented in Chap. 9. In this chapter, the discussion of the opti-

cal properties focuses on the electronic structure, the phonon structure, and

the couplingbetween electrons and phonons in observations of resonance Ra-

man scatteringand related phenomena. The contribution made by electron

spectroscopies to the characterization of the electronic structure of the nano-

tubes is discussed in Chap. 10, in comparison with similar studies devoted to

graphite and C 60 . This is followed in Chap. 11 by a brief review of the phonon

and thermal properties, with emphasis given to studies of the speciﬁc heat

and the thermal conductivity, which are both sensitive to the low-dimensional

aspects of carbon nanotubes. Chapter 12 discusses experiments and theory

on the mechanical properties of carbon nanotubes. Linear elastic parameters,

non-linear instabilities, yield strength, fracture and supra-molecular interac-

tions are all reviewed. Chapter 13 discusses transport measurements, magne-

totransport properties, electron spin resonance, and a variety of other exotic

properties of multiwall nanotubes. The volume concludes in Chap. 14 with

a brief review of the present early status of potential applications of carbon

nanotubes.

Because of the relative simplicity of carbon nanotubes, we expect them to

play an important role in the current rapid expansion of fundamental studies

on nanostructures and their potential use in nanotechnology. This simplicity

allows us to develop detailed theoretical models for predictingnew phenom-

ena connected with these tiny, one-dimensional systems, and then look for

these phenomena experimentally. Likewise, new experimental eﬀects, which

have been discovered at an amazingly rapid rate, have provided stimulus for

further theoretical developments, many of which are expected to be broadly

applicable to nanostructures and nanotechnology research and development.

Cambridge, Massachusetts

Mildred S. Dresselhaus

Yorktown Heights, New York

Gene Dresselhaus

January 2001

Phaedon Avouris

Introduction to Carbon Materials Research

Mildred S. Dresselhaus 1 and Phaedon Avouris 2

1 Currently on leave from the

Department of Electrical Engineering and Computer Science

and Department of Physics

MIT Cambridge, Massachusetts 02139, USA

millie@mgm.mit.edu

2 IBM Research Division, T. J. Watson Research Laboratory

Yorktown Heights, NY 10598, USA

avouris@us.ibm.com

Abstract. A brief historical review of carbon nanotube research is presented and

some basic deﬁnitions relevant to the structure and properties of carbon nanotubes

are provided.

Carbon nanotubes are unique nanostructures that can be considered conceptu-

ally as a prototype one-dimensional (1D) quantum wire. The fundamental building

block of carbon nanotubes is the very long all-carbon cylindrical Single Wall Carbon

Nanotube (SWNT), one atom in wall thickness and tens of atoms around the cir-

cumference (typical diameter ∼ 1.4 nm). Initially, carbon nanotubes aroused great

interest in the research community because of their exotic electronic properties, and

this interest continues as other remarkable properties are discovered and promises

for practical applications develop.

1 Historical Introduction

10nm diameter [ 1 , 2 , 3 , 4 , 5 , 6 ]. However,

no detailed systematic studies of such very thin ﬁlaments were reported in

these early years, and it was not until the observation of carbon nanotubes in

1991 by Iijima of the NEC Laboratory in Tsukuba, Japan (see Fig. 1 )using

High-Resolution Transmission Electron Microscopy (HRTEM) [ 7 ] that the

carbon nanotube ﬁeld was seriously launched. Independently, and at about

the same time (1992), Russian workers also reported the discovery of carbon

nanotubes and nanotube bundles, but generally having a much smaller length

to diameter ratio [ 8 , 9 ].

A direct stimulus to the systematic study of carbon ﬁlaments of very small

diameters came from the discovery of fullerenes by Kroto , Smalley , Curl ,and

coworkers at Rice University [ 10 ]. In fact, Smalley and others speculated

publically in these early years that a single wall carbon nanotube might

be a limiting case of a fullerene molecule. The connection between carbon

M. S. Dresselhaus, G. Dresselhaus, Ph. Avouris (Eds.): Carbon Nanotubes,

Topics Appl. Phys. 80 ,1– 9 (2001)

c Springer-Verlag Berlin Heidelberg 2001

Very small diameter (less than 10nm) carbon ﬁlaments were prepared in

the 1970’s and 1980’s through the synthesis of vapor grown carbon ﬁbers by

the decomposition of hydrocarbons at high temperatures in the presence of

transition metal catalyst particles of

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